This invention relates to novel compositions of an anionic polymerization initiator and an additive which enhance functionalization of living polymer anions; novel compositions of electrophiles and an additive which enhance functionalization of living polymer anions; and processes which employ these compositions, or an additive, for improved efficiency in the functionalization of living polymer anions.
Polymers that contain terminal functional groups are industrially important. One technique to prepare these terminally functionalized polymers is by reaction of a suitable electrophile with a living polymer anion. For numerous examples of end group functionalization chemistry, see Hsieh, H. L.; Quirk, R. P. Anionic Polymerization: Principles and Practical Applications; Marcel Dekker: New York, N.Y., 1996, pages 261-306.
Some of these functionalization reactions are not very efficient, particularly for the preparation of telechelic polymers, due to the formation of a thick gel during the functionalization. This leads to lower capping efficiency. See, for example, U.S. Pat. No. 5,393,843, Example 1, wherein the capping efficiency was only 82%.
A recently reported terminal functionalization technique uses a protected functionalized electrophile. For instance, Nakahama and co-workers have described the reaction of polystyryllithium with the electrophile Brxe2x80x94(CH2)3C(OCH3)3, a protected carboxyl group. See Hirao, A.; Nagahama, H. Ishizone, T.; Nakahama, S. Macromolecules, 1993, 26, 2145. Excellent terminal functionalization of the living anion was achieved ( greater than 95%). Other examples of efficient functionalization with protected functionalized electrophiles are reported in Ueda, K.; Hirao, A.; S. Nakahama, S. Macromolecules, 1990, 23, 939; Tohyarna, M.; Hirao, A.; Nakahama, S. Macromol. Chem. Phys. 1996,197, 3135, and Labeau, M. P.; Cramail, H.; Deffieux, A. Polymer International, 1996, 41, 453.
To obtain efficient functionalization, these functionalization reactions are conducted in tetrahydrofuran (THF) at xe2x88x9280xc2x0 C. THF, however, is an expensive solvent, and these low-temperature conditions are not practical on an industrial scale. In addition, efficient functionalization of polymer anions was only observed with expensive alkyl bromides.
The present invention provides compositions capable of increasing efficiencies in the functionalization of living polymer anions. The compositions include as a component one or more additives, such as an alkali halide or alkali alkoxide. The inventors have unexpectedly found that the additives are capable of improving the efficiency of reactions between polymer anions and electrophiles, as compared to similar reactions in the absence of an additive. In one aspect of the invention, the compositions include one or more additives and one or more anionic polymerization initiators. Exemplary anionic polymerization initiators include non-functionalized and functionalized organoalkali metal initiators. In another aspect of the invention, the compositions include one or more additives and one or more electrophiles useful for functionalizing living polymers.
Processes for improving living polymer anion functionalization are also provided. In this aspect of the invention, a living polymer anion is functionalized using a suitable electrophile in the presence of one or more additives as described above. Higher yields of functionalized polymers were observed when the additive was employed. In addition, the employment of the additive allowed the functionalization to be performed in hydrocarbon solvent at room temperature. Further, these reaction conditions are much less expensive on a commercial scale, as compared to the prior art. The invention can also be used with a variety of monomers and/or functionalizing agents. For example, it was discovered that the less expensive, and more readily available, alkyl chlorides afford efficient functionalization when an additive is employed.
Yet another embodiment of the invention provides novel electrophiles. The novel electrophiles have the formula 
wherein:
X is halogen selected from chloride, bromide and iodide;
Z is a branched or straight chain hydrocarbon connecting group which contains 1-25 carbon atoms, optionally substituted with aryl or substituted aryl;
T is selected from the group consisting of oxygen, sulfur, nitrogen, and mixtures thereof;
(Axe2x80x94R1R2R3) is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of the Elements and R1, R2, and R3 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
R, R4, and R5 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen; and
1 is an integer from 1 to 7.
Additives useful in the invention include, but are not limited to, alkali halides, such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium iodide, potassium chloride, and mixtures thereof; alkali alkoxides, such as lithium t-butoxide, lithium s-butoxide, potassium t-butoxide, and mixtures thereof; and the like and mixtures thereof. The additives should be dried, prior to use.
Several factors influence the amount of additive required, such as the nature of the polymer anion; the identity of the hydrocarbon solvent; the presence of a polar additive (co-solvent); the amount of the polar additive; the nature of the electrophile; and the identity of the additive. An effective amount of the additive employed is from as little as 0.01 equivalents of the electrophile, up to greater than five equivalents again based on the electrophile. In general, less than ten equivalents of the additive are effective for increasing the efficiency of the functionalization reaction.
In one aspect of the invention, the compositions can include one or more organoalkali metal anionic polymerization initiators. Exemplary anionic polymerization initiators include alkyllithium initiatiors represented by the formula Rxe2x80x2-Li, wherein Rxe2x80x2 represents an aliphatic, cycloaliphatic, or arylsubstituted aliphatic radical. Preferably, Rxe2x80x2 is an alkyl or substituted alkyl group of 1-12 carbon atoms. Such initiators include, but are not limited to, methyllithium, ethyllithium, n-propyllithium, 2-propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, n-hexyllithium, 2-ethylhexyllithium, and the like and mixtures thereof. As used herein, alkyllithium initiators also include dilithium initiators as known in the art. See, for example, U.S. Pat. Nos. 5,393,843 and 5,405,911. Dilithium initiators can be prepared by the reaction of an alkyllithium reagent, such as s-butyllithium, with a compound having at least two independently polymerizable vinyl groups, such as the isomeric divinylbenzenes or isomeric diisopropenylbenzenes.
One or more functionalized organoalkali metal initiators may also be employed in the compositions of the invention. These functionalized initiators have the general structure shown below:
Mxe2x80x94Qnxe2x80x94Zxe2x80x94Txe2x80x94(Axe2x80x94R7R8R9)mxe2x80x83xe2x80x83(I)
or 
wherein:
M is an alkali metal selected from the group consisting of lithium, sodium and potassium;
Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the Mxe2x80x94Z linkage;
n is an integer from 0 to 5;
Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
T is selected from the group consisting of oxygen, sulfur, and nitrogen groups and mixtures thereof;
(Axe2x80x94R7R8R9)m is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements, and R7, R8, and R9 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
1 is an integer from 1 to 7; and
m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.
As used herein, the term xe2x80x9calkylxe2x80x9d refers to straight chain and branched C1-C25 alkyl. The term xe2x80x9csubstituted alkylxe2x80x9d refers to C1-C25 alkyl substituted with one or more lower C1-C10 alkyl lower alkoxy, lower alkylthio, or lower dialkylamino. The term xe2x80x9ccycloalkylxe2x80x9d refers to C3-C12 cycloalkyl. The term xe2x80x9csubstituted cycloalkylxe2x80x9d refers to C3-C12 cycloalkyl substituted with one or more lower C1-C10 alkyl lower alkoxy, lower alkylthio, or lower dialkylamino. The term xe2x80x9carylxe2x80x9d refers to C5-C25 aryl having one or more aromatic rings, each of 5 or 6 carbon atoms. Multiple aryl rings may be fused, as in naphthyl or unfused, as in biphenyl. The term xe2x80x9csubstituted arylxe2x80x9d refers to C5-C25 aryl substituted with one or more lower C1-C10 alkyl, lower alkoxy, lower alkylthio, or lower dialkylamino. Exemplary aryl and substituted aryl groups include, for example, phenyl, benzyl, and the like.
U.S. Pat. 5,496,940 and 5,527,753 disclose novel, tertiary amino initiators which are soluble in hydrocarbon solvents. These initiators, useful in practicing this invention, are derived from omega-tertiary-amino-1-haloalkanes of the following general structures:
Xxe2x80x94Zxe2x80x94N(A(R1R2R3))2
and 
wherein X is defined as a halogen, preferably chlorine or bromine; Z is defined as a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms; A is an element selected from Group IVa of the Periodic Table of the Elements, R1, R2 and R3 are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamnino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms, and m is an integer from 1 to 7. The process reacts selected omega-tertiary-amino-1-haloalkanes whose alkyl groups contain 3 to 25 carbon atoms, with lithium metal at a temperature between about 35xc2x0 C. and about 130xc2x0 C., preferably at the reflux temperature of an alkane, cycloalkane, or aromatic reaction solvent containing 5 to 10 carbon atoms and mixtures of such solvents.
Tertiary amino-1-haloalkanes useful in the practice of this invention include, but are not limited to, 3-(N,N-dimethylamino)-1-propyl halide, 3-(N,N-dimethylamino)-2-methyl-1-propyl halide, 3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl halide, 4-(N,N-dimethylamino)-1-butyl halide, 5-(N,N-dimethylamino)-1-pentyl halide, 6-(N,N-dimethylamino)-1-hexyl halide, 3-(N,N-diethylamino)-1-propyl halide, 3-(N,N-diethylamino)-2-methyl-1-propyl halide, 3-(N,N-diethylamino)-2,2-dimethyl-1-propyl halide, 4-(N,N-diethylamino)-1-butyl halide, 5-(N,N-diethylamino)-1-pentyl halide, 6-(N,N-diethylamino)-1-hexyl halide, 3-(N-ethyl-N-methylamino)-1-propyl halide, 3-(N-ethyl-N-methylamino)-2-methyl-1-propyl halide, 3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-propyl halide, 4-(N-ethyl-N-methylamino)-1-butyl halide, 5-(N-ethyl-N-methylamino)-1-pentyl halide, 6-(N-ethyl-N-methylamino)-1-hexyl halide, 3-(piperidino)-1-propyl halide, 3-(piperidino)-2-methyl-1-propyl halide, 3-(piperidino)-2,2-dimethyl-1-propyl halide, 4-(piperidino)-1-butyl halide, 5-(piperidino)-1-pentyl halide, 6-(piperidino)-1-hexyl halide, 3-(pyrrolidino)-1-propyl halide, 3-(pyrrolidino)-2-methyl-1-propyl halide, 3-(pyrrolidino)-2,2-dimethyl-1-propyl halide, 4-(pyrrolidino)-1-butyl halide, 5-(pyrrolidino)-1-pentyl halide, 6-(pyrrolidino)-1-hexyl halide, 3-(hexamethyleneimino)-1-propyl halide, 3-(hexamethyleneimino)-2-methyl-1-propyl halide, 3-(hexamethyleneimino)-2,2-dimethyl-1-propyl halide, 4-(hexamethyleneimino)-1-butyl halide, 5-(hexamethyleneimino)-1-pentyl halide, 6-(hexamethyleneimino)-1-hexyl halide, 3-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-propyl halide, 4-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-butyl halide, 6-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-hexyl halide, 3-(N-isopropyl-N-methyl)-1-propyl halide, 2-(N-isopropyl-N-methyl)-2-methyl-1-propyl halide, 3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-propyl halide, and 4-(N-isopropyl-N-methyl)-1-butyl halide. The halo- or halide group is selected from chlorine and bromine.
U.S. Pat. No. 5,600,021 discloses novel monofunctional ether initiators which are soluble in hydrocarbon solvents. These initiators, useful in practicing this invention, are derived from omega-protected-hydroxy-1-haloalkanes of the following general structure:
Xxe2x80x94Zxe2x80x94Oxe2x80x94Cxe2x80x94R1R2R3)
wherein X is defined as a halogen, preferably chlorine or bromine; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, R1, R2 and R3 are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms. The process reacts selected omega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25 carbon atoms, with lithium metal at a temperature between about 35xc2x0 C. and about 130xc2x0 C., preferably at the reflux temperature of an alkane, cycloalkane, or aromatic reaction solvent containing 5 to 10 carbon atoms and mixtures of such solvents.
The precursor omega-protected-1-haloalkanes (halides) were prepared from the corresponding haloalcohol by the standard literature methods. For example, 3-(1,1-dimethylethoxy)-1-chloropropane was synthesized by the reaction of 3-chloro-1-propanol with 2-methylpropene according to the method of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters, 29, 1988, 2951. The method of B. Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5:893, which involved the reaction of the appropriate alcohol with 2-methyl-2-butene catalyzed by boron trifluoride etherate is employed for the preparation of the t-amyl ethers. The alkoxy, alkylthio or dialkylamino substituted ethers, for example 6-[3-(methylthio)-1-propyloxy]-1-chlorohexane, were synthesized by reaction of the corresponding substituted alcohol, for instance 3-methylthio-1-propanol, with an alpha-bromo-omega-chloroalkane, for instance 1-bromo-6-hexane, according to the method of J. Almena, F. Foubelo and M. Yus, Tetrahedron, 51, 1995, 11883. The compound 4-(methoxy)-1-chlorobutane, and the higher analogs, were synthesized by the ring opening reaction of tetrahydrofuran with thionyl chloride and methanol, according to the procedure of T. Ferrari and P. Vogel, SYNLETT, 1991, 233. The triphenylmethyl protected compounds, for example 3-(triphenylmethoxy)-1-chloropropane, are prepared by the reaction of the haloalcohol with triphenylmethylchloride, according to the method of S. K. Chaudhary and O. Hernandez, Tetrahedron Letters, 1979, 95.
Omega-hydroxy-protected-1-haloalkanes prepared in accord with this earlier process useful in practicing this invention can include, but are not limited to, 3-(1,1-dimethylethoxy)-1-propyl halide, 3-(1,1-dimethylethoxy)-2-methyl-1-propyl halide, 3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyl halide, 4-(1,1-dimethylethoxy)-1-butyl halide, 5-(1,1-dimethylethoxy)-1-pentyl halide, 6-(1,1-dimethylethoxy)-1-hexyl halide, 8-(1,1-dimethylethoxy)-1-octyl halide, 3-(1,1-dimethylpropoxy)-1-propyl halide, 3-(1,1-dimethylpropoxy)-2-methyl-1-propyl halide, 3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyl halide, 4-(1,1-dimethylpropoxy)-1-butyl halide, 5-(1,1-dimethylpropoxy)-1-pentyl halide, 6-(1,1-dimethylpropoxy)-1-hexyl halide, 8-(1,1-dimethylpropoxy)-1-octyl halide, 4-(methoxy)-1-butyl halide, 4-(ethoxy)-1-butyl halide, 4-(propyloxy)-1-butyl halide, 4-(1-methylethoxy)-1-butyl halide, 3-(triphenylmethoxy)-2,2-dimethyl-1-propyl halide, 4-(triphenylmethoxy)-1-butyl halide, 3-[3-(dimethylamino)-1-propyloxy]-1-propyl halide, 3-[2-(dimethylamino)-1-ethoxy]-1-propyl halide, 3-[2-(diethylamino)-1-ethoxy]-1-propyl halide, 3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyl halide, 3-[2-(1-piperidino)-1-ethoxy]-1-propyl halide, 3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyl halide, 4-[3-(dimethylamino)-1-propyloxy]-1-butyl halide, 6-[2-(1-piperidino)-1-ethoxy]-1-hexyl halide, 3-[2-(methoxy)-1-ethoxy]-1-propyl halide, 3-[2-(ethoxy)-1-ethoxy]-1-propyl halide, 4-[2-(methoxy)-1-ethoxy]-1-butyl halide, 5-[2-(ethoxy)-1-ethoxy]-1-pentyl halide, 3-[3-(methylthio)-1-propyloxy]-1-propyl halide, 3-[4-(methylthio)-1-butyloxy]-1-propyl halide, 3-(methylthiomethoxy)-1-propyl halide, 6-[3-(methylthio)-1-propyloxy]-1-hexyl halide, 3-[4-(methoxy)-benzyloxy]-1-propyl halide, 3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyl halide, 3-[2,4-(dimethoxy)-benzyloxy]-1-propyl halide, 8-[4-(methoxy)-benzyloxy]-1-octyl halide, 4-[4-(methylthio)-benzyloxy]-1-butyl halide, 3-[4-(dimethylamino)-benzyloxy]-1-propyl halide, 6-[4-(dimethylamino)-benzyloxy]-1-hexyl halide, 5-(triphenylmethoxy)-1-pentyl halide, 6-(triphenylmethoxy)-1-hexyl halide, and 8-(triphenylmethoxy)-1-octyl halide. The halo- or halide group is selected from chlorine and bromine.
U.S. Pat. No. 5,362,699 discloses novel monofunctional silyl ether initiators which are soluble in hydrocarbon solvents. These initiators, useful in practicing this invention, are derived from omega-silyl-protected-hydroxy-1-haloalkanes of the following general structure:
Xxe2x80x94Zxe2x80x94Oxe2x80x94Sixe2x80x94R1R2R3)
wherein X is defined as a halogen, preferably chlorine or bromine; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; and R1, R2, and R3 are independently defined as saturated and unsaturated aliphatic and aromatic radicals, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent optionally containing a Lewis base. The process reacts selected omega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25 carbon atoms, with lithium metal at a temperature between about 25xc2x0 C. and about 40xc2x0 C., in an alkane, cycloalkane or aromatic reaction solvent containing 5 to 10 carbon atoms and mixtures of such solvents.
t-Butyldimethylsilyl protected compounds, for example 4-(t-butyldimethylsilyloxy)-1-butylhalide, are prepared from t-butyldimethylchlorosilane, and the corresponding halo-alcohol, according to the method described in U.S. Pat. No. 5,493,044. Omega-silyloxy-1-haloalkanes prepared in accord with this earlier process useful in practicing this invention can include, but are not limited to, 3-(t-butyldimethylsilyloxy)-1-propyl halide, 3-(t-butyldimethyl-silyloxy)-2-methyl-1-propyl halide, 3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl halide, 4-(t-butyldimethylsilyloxy)-1-butyl halide, 5-(t-butyldimethyl-silyloxy)-1-pentyl halide, 6-(t-butyldimethylsilyloxy)-1-hexyl halide, 8-(t-butyldimethylsilyloxy)-1-octyl halide, 3-(t-butyldiphenylylsilyloxy)-1-propyl halide, 3-(t-butyldiphenylylsilyloxy)-2-methyl-1-propyl halide, 3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-propyl halide, 6-(t-butyldimethylsilyloxy)-1-hexyl halide, and 3-(trimethylsilyloxy)-2,2-dimethyl-1-propyl halide. The halo- or halide group is selected from chlorine and bromine.
Monofunctional thioether initiators useful in the practice of this invention are derived from omega-protected-thio-1-haloalkanes of the following general structure:
Xxe2x80x94Zxe2x80x94Sxe2x80x94(Axe2x80x94R1R2R3)
wherein X is defined as a halogen, preferably chlorine or bromine; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms; (Axe2x80x94R1R2R3) is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements; R1, R2, and R3 are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms. The process reacts selected omega-thioprotected-1-haloalkyls whose alkyl groups contain 3 to 25 carbon atoms, with lithium metal at a temperature between about 35xc2x0 C. and about 130xc2x0 C., preferably at the reflux temperature of an alkane, cycloalkane or aromatic reaction solvent containing 5 to 10 carbon atoms and mixtures of such solvents.
The initiator precursor, omega-thio-protected-1-haloalkanes (halides), are prepared from the corresponding halothiol by the standard literature methods. For example, 3-(1,1-dimethylethylthio)-1-propylchloride is synthesized by the reaction of 3-chloro-1-propanthiol with 2-methylpropene according to the method of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters, 29, 1988, 2951. Alternatively, reaction of 1,1-dimethylethylthiol with 1-bromo-3-chloropropane and a base affords 3-(1,1-dimethylethylthio)-1-propylchloride. The method of B. Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5893, which involved the reaction of the appropriate thiol with 2-methyl-2-butene catalyzed by boron trifluoride etherate is employed for the preparation of the t-amyl thioethers. Additionally, 5-(cyclohexylthio)-1-pentylhalide and the like, can be prepared by the method of J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51, 1995, 11883. This synthesis involves the reaction of the appropriate thiol with an alkyllithium, then reaction of the lithium salt with the corresponding alpha, omega dihalide. 3-(Methylthio)-1-propylchloride can be prepared by chlorination of the corresponding alcohol with thionyl chloride, as taught by D. F. Taber and Y. Wang, J. Org, Chem., 58, 1993, 6470. Methoxymethylthio compounds, such as 6-(methoxymethylthio)-1-hexylchloride, are prepared by the reaction of the omega-chloro-thiol with bromochloromethane, methanol, and potassium hydroxide, by the method of F. D. Toste and I. W. J. Still, Synlett, 1995, 159. t-Butyldimethylsilyl protected compounds, for example 4-(t-butyldimethylsilylthio)-1-butylhalide, are prepared from t-butyldimethylchlorosilane, and the corresponding thiol, according to the method described in U.S. Pat. No. 5,493,044.
Omega-thio-protected 1-haloalkanes prepared in accord with this earlier process useful in practicing this invention can include, but are not limited to, 3-(methylthio)-1-propylhalide, 3-(methylthio)-2-methyl-1-propylhalide, 3-(methylthio)-2,2-dimethyl-1-propylhalide, 4-(methylthio)-1-butylhalide, 5-(methylthio)-1-pentylhalide, 6-(methylthio)-1-hexylhalide, 8-(methylthio)-1-octylhalide, 3-(methoxymethylthio)-1-propylhalide, 3-(methoxymethylthio)-2-methyl-1-propylhalide, 3-(methoxymethylthio)-2,2-dimethyl-1-propylhalide, 4-(methoxymethylthio)-1-butylhalide, 5-(methoxymethylthio)-1-pentylhalide, 6-(methoxymethylthio)-1-hexylhalide, 8-(methoxymethylthio)-1-octylhalide, 3-(1,1-dimethylethylthio)-1-propylhalide, 3-(1,1-dimethylethylthio)-2-methyl-1-propylhalide, 3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propylhalide, 4-(1,1-dimethylethylthio)-1-butylhalide, 5-(1,1-dimethylethylthio)-1-pentylhalide, 6-(1,1-dimethylethylthio)-1-hexylhalide, 8-(1,1-dimethylethylthio)-1-octylhalide, 3-(1,1-dimethylpropylthio)-1-propylhalide, 3-(1,1-dimethylpropylthio)-2-methyl-1-propylhalide, 3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propylhalide, 4-(1,1-dimethylpropylthio)-1-butylhalide, 5-(1,1-dimethylpropylthio)-1-pentylhalide, 6-(1,1-dimethylpropylthio)-1-hexylhalide, 8-(1,1-dimethylpropylthio)-1-octylhalide, 3-(cyclopentylthio)-1-propylhalide, 3-(cyclopentylthio)-2-methyl-1-propylhalide, 3-(cyclopentylthio)-2,2-dimethyl-1-propylhalide, 4-(cyclopentylthio)-1-butylhalide, 5-(cyclopentylthio)-1-pentylhalide, 6-(cyclopentylthio)-1-hexylhalide, 8-(cyclopentylthio)-1-octylhalide, 3-(cyclohexylthio)-1-propylhalide, 3-(cyclohexylthio)-2-methyl-1-propylhalide, 3-(cyclohexylthio)-2,2-dimethyl-1-propylhalide, 4-(cyclohexylthio)-1-butylhalide, 5-(cyclohexylthio)-1-pentylhalide, 6-(cyclohexylthio)-1-hexylhalide, 8-(cyclohexylthio)-1-octylhalide, 3-(t-butyldimethylsilylthio)-1-propylhalide, 3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide, 3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propylhalide, 3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide, 4-(t-butyldimethylsilylthio)-1-butylhalide, 6-(t-butyldimethylsilylthio)-1-hexylhalide and 3-(trimethylsilylthio)-2,2-dimethyl-1-propylhalide. The halo- or halide group is selected from chlorine and bromine.
Functionalized organoalkali metal initiators of the following structures may also be employed in the compositions of the invention: 
wherein:
M is an alkali metal;
R10 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl; and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
R11 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl; saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl; saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl; and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
R12 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl; saturated and unsaturated C3xe2x80x94C25 cycloalkyl; saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl; and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms;
Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the Mxe2x80x94R12 linkage; and
n is an integer from 1 to 5. See pending U.S. application Ser. No. 09/139,222, filed Aug. 24, 1998, the entire disclosure of which is hereby incorporated by reference.
The tertiary amino initiators of this invention are prepared by reaction of selected tertiary amino halides, such as described in structure (IX), with an alkali metal selected from lithium, sodium and potassium, for example at a temperature ranging from about 35 to 130xc2x0 C., advantageously at an elevated temperature ( greater than 40xc2x0 C.), in a hydrocarbon solvent containing five to ten carbon atoms and mixtures of such solvents to form an alkylorganometallic compound containing a tertiary amine. 
wherein:
X is halogen selected from the group consisting of chlorine, bromine and iodine; and R10, R11, and R12 are as defined above. These halides are commercially available or can be prepared using techniques known in the art.
Examples of tertiary amino halides useful in the practicing this invention include, but are not limited to, 2-(2-chloroethyl)-N-methylpiperidine, 2-(2-chloroethyl)-N-ethylpiperidine, 2-(2-chloroethyl)-N-propylpiperidine, 2-(2-chloroethyl)-N-methylpyrrolidine, 2-(2-chloroethyl)-N-ethylpyrrolidine, 3-(chloromethyl)-N-methylpiperidine, 3-(chloromethyl)-N-ethylpiperidine, 4-(2-chloroethyl)-N-methylpiperidine, 4-(2-chloroethyl)-N-ethylpiperidine, 4-(2-chloroethyl)-N-propylpiperidine, 4-(chloromethyl)-N-methylpiperidine, 4-(chloromethyl)-N-ethylpiperidine, 4-(chloromethyl)-N-propylpiperidine, 2-(2-chloroethyl)-N-methylhexarnethyleneimine, 2-(2-chloroethyl)-N-methylmorpholine, and mixtures thereof.
The chain extended compounds of structure (VIII) can have greater solubility in hydrocarbon solution than the compounds described in structure (VII). For example, the solubility of 2-(2-lithioethyl)-N-methyl-piperidine in cyclohexane solution was about 6 weight percent. However, when this same material was chain extended with two equivalents of isoprene, the solubility increased to over 28 weight percent. Similar increases in solubility were observed for other chain extended analogues.
The initiators described in structure (VIII) are prepared by reacting an organometallic compound of the formula described in structure (VII) wherein M, R10, R11, and R12 have the meanings ascribed above, with one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds, to form an extended hydrocarbon chain between M and R12 in structure (VIII), which extended chain is denoted as Qn in structure (VIII). The compounds of structure (VIII) are prepared by first reacting in an inert solvent a selected tertiary amino halide (structure (IX)) with an alkali metal at a temperature ranging from about 35xc2x0 C. to about 130xc2x0 C., advantageously at a temperature above about 40xc2x0 C., to afford an organometallic compound of structure (VII), which is then optionally reacted with a one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds, in a predominantly alkane, cycloalkane, or aromatic reaction solvent, which solvent contains 5 to 10 carbon atoms, and mixtures of such solvents to produce an initiator with an extended chain or tether between the metal atom (M) and R12 in structure (VIII) above and mixtures thereof with compounds of structure (VII).
Incorporation of Q groups into the Mxe2x80x94R12 linkage to form the compounds of structure (VIII) above involves addition of compounds of structure (VII) across the carbon to carbon double bonds in compounds selected from the consisting of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds to produce new carbon-lithium bonds of an allylic or benzylic nature, similar to those found in a propagating polyalkadiene or polyarylethylene polymer chain derived by anionic initiation of the polymerization of conjugated dienes or arylethylenes. These new carbon-lithium bonds are now xe2x80x9cactivatedxe2x80x9d toward polymerization and so are much more efficient in promoting polymerization than the precursor Mxe2x80x94R12 (Mxe2x95x90Li) bonds themselves.
In another aspect of the invention, the compositions include one or more additives and one or more electrophiles. The electrophiles can, for example, include one or more functionalized alkyl halides (electrophiles). Co-pending U.S. patent application Ser. Nos. 08/872,895, 08/873,220, and 08/893,951, incorporated herein by reference, detail the synthesis of telechelic and functionalized star polymers by the reaction of living polymer anions with electrophiles of the following general structure:
Xxe2x80x94Zxe2x80x94Txe2x80x94(Axe2x80x94R7R8R9)mxe2x80x83xe2x80x83(III)
or 
wherein:
X is halogen selected from the group consisting of chloride, bromide and iodide;
Z is a branched or straight chain hydrocarbon connecting group which contains 1-25 carbon atoms, optionally containing aryl or substituted aryl groups;
T is selected from the group consisting of oxygen, sulfur, and nitrogen groups and mixtures thereof;
(Axe2x80x94R7R8R9)m is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements, and R7, R8, and R9 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and
1 is an integer from 1 to 7.
Examples of electrophiles of this class include, but are not limited to, 3-(N,N-dimethylamino)-1-chloropropane, 3-(N,N-dimethylamino)-1-bromopropane, 3-(N,N-dimethylamino)-2-methyl-1-chloropropane, 3-(N,N-dimethylamino)-2,2-dimethyl-1-chloropropane, 4-(N,N-dimethylamino)-1-chlorobutane, 5-(N,N-dimethylamino)-1-chloropentane, 3-(N,N-diethylamino)-2-methyl-1-chloropropane, 3-(N-ethyl-N-methylamino)-1-chloropropane, 6-(N,N-dimethylamino)-1-chlorohexane, 3-(N,N-diethylamino)-1-chloropropane, 3-(N,N-diethylamino)-2,2-dimethyl-1-chloropropane, 4-(N,N-diethylamino)-1-chlorobutane, 5-(N,N-diethylarnino)-1-chloropentane, 6-(N,N-diethylamino)-1-chlorohexane, 3-(N-ethyl-N-methylamino)-2-methyl-1-chloropropane, 3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-chloropropane, 4-(N-ethyl-N-methylamino)-1-chlorobutane, 5-(N-ethyl-N-methylamino)-1-chloropentane, 6-(N-ethyl-N-methylamino)-1-chlorohexane, 3-(piperidino)-1-chloropropane, 3-(piperidino)-2-methyl-1-chloropropane, 3-(piperidino)-2,2-dimethyl-1-chloropropane, 4-(piperidino)-1-chlorobutane, 5-(piperidino)-1-chloropentane, 6-(piperidino)-1-chlorohexane, 3-(pyrrolidino)-1-chloropropane, 3-(pyrrolidino)-2-methyl-1-chloropropane, 3-(pyrrolidino)-2,2-dimethyl-1-chloropropane, 4-(pyrrolidino)-1-chlorobutane, 5-(pyrrolidino)-1-chloropentane, 6-(pyrrolidino)-1-chlorohexane, 3-(hexamethyleneimino)-1-chloropropane, 3-(hexamethyleneimino)-2-methyl-1-chloropropane, 3-(hexamethyleneimino)-2,2-dimethyl-1-chloropropane, 4-(hexamethyleneimino)-1-chlorobutane, 5-(hexamethyleneimino)-1-chloropentane, 6-(hexamethyleneimino)-1-chlorohexane, 3-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chloropropane, 4-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chlorobutane, 6-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chlorohexane, 3-(N-isopropyl-N-methyl)-1-chloropropane, 2-(N-isopropyl-N-methyl)-2-methyl-1-chloropropane, 3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-chloropropane, 4-(N-isopropyl-N-methyl)-1-chlorobutane, 3-(1,1-dimethylethoxy)-1-chloropropane, 3-(1,1-dimethylethoxy)-1-bromopropane, 3-(1,1-dimethylethoxy)-2-methyl-1-chloropropane, 3-(1,1-dimethylethoxy)-2,2-dimethyl-1-chloropropane, 4-(1,1-dimethylethoxy)-1-chlorobutane, 5-(1,1-dimethylethoxy)-1-chloropentane, 6-(1,1-dimethylethoxy)-1-chlorohexane, 8-(1,1-dimethylethoxy)-1-chlorooctane, 3-(1,1-dimethylpropoxy)-1-chloropropane, 3-(1,1-dimethylpropoxy)-2-methyl-1-choropropane, 3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-chlorpropane, 3-(t-butyldimethylsilyloxy)-1-chloropropane, 3-(t-butyldimethylsilyloxy)-2-methyl-1-chloropropane, 3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-chloropropane, 4-(t-butyldimethylsilyloxy)-1-chlorobutane, 4-(t-butyldimethylsilyloxy)-1-iodobutane, 5-(t-butyldimethylsilyloxy)-1-chloropentane, 6-(t-butyldimethylsilyloxy)-1-chlorohexane, 8-(t-butyldimethylsilyloxy)-1-chlorooctane, 3-(t-butyldiphenylylsilyloxy)-1-chloropropane, 3-(t-butyldiphenylylsilyloxy)-2-methyl-1-chloropropane, 3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-chloropropane, 6-(t-butyldimethylsilyloxy)-1-chlorohexane, 3-(triethylsilyloxy)-2,2-dimethyl-1-chloropropane, 3-(trimethylsilyloxy)-2,2-dimethyl-1-bromopropane and 3-(trimethylsilyloxy)-2,2-dimethyl-1-chloropropane, 3-(methylthio)-1-chloropropane, 3-(methylthio)-1-bromopropane, 3-(methylthio)-2-methyl-1-chloropropane, 3-(methylthio)-2,2-dimethyl-1-chloropropane, 4-(methylthio)-1-chlorobutane, 5-(methylthio)-1-chloropentane, 6-(methylthio)-1-chlorohexane, 8-(methylthio)-1-chlorooctane, 3-(methoxymethylthio)-1-chloropropane, 3-(methoxymethylthio)-2-methyl-1-chloropropane, 3-(methoxymethylthio)-2,2-dimethyl-1-chloropropane, 4-(methoxymethylthio)-1-chlorobutane, 5-(methoxymethylthio)-1-chloropentane, 3-(1,1-dimethylpropylthio)-1-chloropropane, 3-(1,1-dimethylpropylthio)-2-methyl-1-chloropropane, and 3-(t-butyldimethylsilylthio)-1-chloropropane.
Functionalizing agents, or electrophiles, of the formula Xxe2x80x94Zxe2x80x94Txe2x80x94(Axe2x80x94R7R8R9)m or 
can be prepared as described, for example, in International Publication WO 97/16465. In addition, the electrophiles can be prepared as described in K. Ueda, A. Hirao, and S. Nakahama, Macromolecules, 23, 939 (1990); U.S. Pat. No. 5,496,940; U.S. Pat. No. 5,600,021; U.S. Pat. No. 5,362,699; A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters, 29, 1988, 2951; B. Figadere, X. Franck, and A. Cave, Tetrahedron Letters, 34, 1993, 5893; J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51, 1995, 11883; D. F. Taberand Y. Wang, J. Org. Chem., 58, 1993, 6470; F. D. Toste and I. W. J. Still, Synlett, 1995, 159; and U.S. Pat. No. 5,493,044.
Additional electrophiles that are useful in the practice of this invention include: 
wherein:
X is a halogen selected from chloride, bromide and iodide;
Z is a branched or straight chain hydrocarbon connecting group which contains 1-25 carbon atoms, optionally substituted with aryl or substituted aryl;
T is selected from the group consisting of oxygen, sulfur, nitrogen, and mixtures thereof;
(Axe2x80x94R1R2R3) is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of the Elements and R1, R2, and R3 are each independently selected form the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
R, R4, and R5 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen;
1 is an integer from 1 to 7;
m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and
n is 2 or 3.
Examples of electrophiles of this class include, but are not limited to, trimethyl 4-bromoorthobutyrate, trimethyl 3-chloroorthopropionate, 5-chloro-2-pentanone ethylene ketal, triethyl 5-chloroorthopentanoate, N-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane, and the like and mixtures thereof.
These electrophiles can be prepared by standard literature procedures. For example, triethyl ortho-3-chloropropionate can be prepared from 3-chloroprionitrile by the method of G. Casy, J. W. Patterson, and R. J. K. Taylor, Org. Syn. Coll. Vol. 8, 415 (1993). Substituted dimethyl or diethyl dithio acetals and ketals can be prepared from the corresponding halo aldehydes or halo ketones and methylthiol or ethylthiol and HCl catalyst, as described by H. Zinner, Chem. Ber., 83, 275 (1980). Halo substituted 1,3-dithianes can be synthesized from the corresponding halo carbonyl compound, 1,3-propanedithiol, and boron trifluoride etherate catalyst, as detailed by J. A. Marshall and J. L. Belletire, Tetrahedron Letters, 871 (1971). Analogously, halo substituted 1,3-dithiolanes can be synthesized from the corresponding halo carbonyl compound, 1,3-ethanedithiol, and boron trifluoride etherate catalyst, as detailed by R. P. Hatch, J. Shringarpure, and S. M. Weinreb, J Org. Chem., 43, 4172 (1978). Substituted dimethyl or diethyl acetals and ketals can be prepared from the corresponding halo aldehydes or halo ketones and methanol or ethanol and anhydrous HCl catalyst, as described by A. F. B. Cameron, J. S. Hunt, J. F. Oughton, P. A. Wilkinson, and B. M. Wilson, J Chem. Soc., 3864 (1953). The method of R. A. Daignault and E. L. Eliel, Org. Syn. Col. Vol. V, 303, (1973), which involves the reaction of a halo-substituted aldehyde or ketone with ethylene glycol, with paratolunesulfonic acid catalyst and azeotropic removal of water, can be employed to prepare the corresponding halo-substituted 1,3-dioxolane. Halo-substituted 1,3-dioxanes can be prepared from the corresponding halo aldehyde or ketone, 1,3-propanediol, paratoluenesulfonic acid catalyst, with azeotropic removal of water, see J. E. Cole, W. S. Johnson, P. A. Robins, and J. Walker, J Chem. Soc., 244 (1962), and H. Okawara, H. Nakai, and M. Ohno, Tetrahedron Letters, 23, 1087 (1982). The reaction of 2-mercaptoethanol with a halo-substituted aldehyde or ketone, with zinc chloride catalyst affords the commensurate substituted 1,3-oxathiolane, as reported by J. Romo, G. Rosenkranz, and C. Djerassi, J Amer. Chem. Soc., 73, 4961 (1951) and V. K. Yadav and A. G. Fallis, Tetrahedron Letters, 29, 897 (1988). Substituted oxazolidines can be synthesized from the corresponding aminoalcohol and a halo-substituted aldehyde or ketone, see E. P. Goldberg and H. R. Nace, J Amer. Chem. Soc., 77, 359 (1955). In a similar fashion, the method of A. J. Carpenter and D. J. Chadwick, Tetrahedron, 41, 3803 (1985) can be employed to generate N,Nxe2x80x2-dimethylimidazolidines from a halo aldehyde or ketone and N,Nxe2x80x2-dimethyl-1,2-ethylenediamine. Higher homologs can be prepared from the parent halo-substituted imidazolidine via dialkylation, see J. C. Craig and R. J. Young, Org. Syn. Coll. Vol. V, 88 (1973). N-3-Chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane can be prepared by the reaction of 3-chloropropylamine and 1,1,4,4-tetramethyl-1,4-dichlorodisilethylene and an acid acceptor, see S. Djuric, J. Venit, and P. Magnus, Tetrahedron Letters, 22, 1787 (1981).
An additional class of electrophile that is useful in the practice of this invention is described by the general formula:
Xxe2x80x94Zxe2x80x94Sixe2x80x94[Txe2x80x94Axe2x80x94R1R2R3)m]nxe2x80x83xe2x80x83(VI)
wherein:
X is halogen selected from the group consisting of chloride, bromide and iodide;
Z is a branched or straight chain hydrocarbon connecting group which contains 1-25 carbon atoms, optionally substituted with aryl or substituted aryl;
T is selected from the group consisting of oxygen, sulfur, and nitrogen groups and mixtures thereof;
A is an element selected from Group IVa of the Periodic Table of the Elements;
R1, R2, and R3 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and
n is 2 or 3.
Examples of electrophiles of this class include, but are not limited to, 3-chloropropyltrimethoxysilane, chloromethyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 3-chloropropyl-tris(dimethylamino)silane, and the like and mixtures thereof.
An additional class of electrophile that is useful in the practice of this invention is described by the general formula: 
wherein:
Zxe2x80x2 is a halogen atom;
R13 is selected from the group consisting of organic groups containing from 1 to about 12 carbon atoms and a bridging bond;
each R14 is independently selected from the group consisting of hydrogen, organic groups containing from 1 to about 12 carbon atoms and a bridging bond;
each R15 is independently selected from the group consisting of hydrogen, organic groups containing from 1 to about 12 carbon atoms;
a is an integer from 4 to about 16; and
b is an integer from 0 to about 12.
See U.S. Pat. No. 5,736,617.
Other compounds useful in functionalizing polymeric living polymers include, but are not limited to, alkylene oxides, such as ethylene oxide, propylene oxide, styrene oxide, and oxetane; oxygen; sulfur; carbon dioxide; halogens such as chlorine, bromine and iodine; propargyl halides; alkenylhalosilanes and omega-alkenylarylhalosilanes, such as styrenyldimethyl chlorosilane; sulfonated compounds, such as 1,3-propane sultone; amides, including cyclic amides, such as caprolactam, N-benzylidene trimethylsilylamide, and dimethyl form amide; silicon acetals; 1,5-diazabicyclo[3.1.0]hexane; allyl halides, such as allyl bromide and allyl chloride; methacryloyl chloride; amines, including primary, secondary, tertiary and cyclic amines, such as 3-(dimethylamino)-propyl chloride and N-(benzylidene)trimethylsilylamine; epihalohydrins, such as epichlorohydrin, epibromohydrin, and epiiodohydrin, and other materials as known in the art to be useful for terminating or end capping polymers. These and other useful functionalizing agents are described, for example, in U.S. Pat. Nos. 3,786,116 and 4,409,357, the entire disclosure of each of which is incorporated herein by reference.
The impact of the additive was initially studied in the functionalization reaction of poly(styryl)lithium. The living polymer anion was treated with 1.5 molar equivalents of 3-(N,N-dimethylamino)-1-chloropropane (Examples 1 and 2). The degree of functionalization was determined by end group titration. The results, tabulated below, indicate that the efficiency of the functionalization reaction increased by approximately 40% by the addition of 1.5 equivalents of dry lithium chloride. Similar results were observed for the functionalization of poly(isoprenyl) lithium (Examples 3 and 4). The functionalization efficiency increased by greater than 25% when the additive, lithium chloride, was employed.
This invention also provides processes for preparing functionalized polymers. In the processes of the invention, an additive as described above is used to improve the functionalization of polymer anions with electrophiles, including alkyl halide electrophiles. The processes for the anionic polymerization of anionically polymerizable monomers comprise initiating polymerization of a conjugated diene hydrocarbon monomer, a mixture of conjugated diene monomers, an alkenylsubstituted aromatic compound, a mixture of alkenylsubstituted aromatic compounds, or a mixture of one or more conjugated diene hydrocarbons and one or more alkenylsubstituted aromatic compounds in a hydrocarbon or mixed hydrocarbon-polar solvent medium at a temperature of 10xc2x0 C. to 150xc2x0 C. with one or more initiators having the formula: 
wherein M, Q, Z, A, Rxe2x80x2, R7, R8, R9, R10, R11, R12, 1, m, and n are as defined above to produce an intermediate living polymer. The monomers can be polymerized singly, sequentially or as a mixture thereof.
The intermediate living polymer is then reacted with one or more electrophiles, such as those described above, in the presence of an additive, also as described above. The resultant linear or branched monofunctional, homotelechelic, heterotelechelic, polymer having one or more terminal functional groups can be recovered.
The additive, or mixture of additives, can be added to the reactor at the beginning of the polymerization, as a component of the initiator composition, during the polymerization, after the polymerization but prior to the functionalization, or as a component of the functionalization formulation.
Monomer(s) to be anionically polymerized to form living polymer anions can be selected from any suitable monomer capable of anionic polymerization, including conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof. Examples of suitable conjugated alkadienes include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, and 2-methyl-3-isopropyl-1,3-butadiene.
Examples of polymerizable alkenylsubstituted aromatic hydrocarbons include, but are not limited to, styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphthalene, 1,2-diphenyl-4-methyl-1-hexene and mixtures of these, as well as alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl derivatives thereof in which the total number of carbon atoms in the combined hydrocarbon constituents is generally not greater than 18. Examples of these latter compounds include 3-methylstyrene, 3,5-diethylstyrene, 4-tert-butylstyrene, 2-ethyl-4-benzylstyrene, 4-phenylstyrene, 4-p-tolylstyrene, 2,4-divinyltoluene and 4,5-dimethyl-1-vinylnaphthalene. U.S. Pat. No. 3,377,404, incorporated herein by reference in its entirety, discloses suitable additional alkenylsubstituted aromatic compounds.
The inert solvent is preferably a non-polar solvent such as a hydrocarbon, since anionic polymerization in the presence of such non-polar solvents is known to produce polyenes with high 1,4-contents from 1,3-dienes. Inert hydrocarbon solvents useful in practicing this invention include but are not limited to inert liquid alkanes, cycloalkanes and aromatic solvents and mixtures thereof. Exemplary alkanes and cycloalkanes include those containing five to 10 carbon atoms, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, methylcycloheptane, octane, decane and the like and mixtures thereof. Exemplary aryl solvents include those containing six to ten carbon atoms, such as toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, and the like and mixtures thereof.
Polar modifiers can be added to the polymerization reaction to alter the microstructure of the resulting polymer, i.e., increase the proportion of 1,2 (vinyl) microstructure or to promote functionalization or randomization. Examples of polar modifiers include, but are not limited to: diethyl ether, dibutyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, methyl tert-butyl ether (MTBE), diazabicyclo[2.2.2]octane (DABCO), triethylamine, tri-n-butylamine, N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine (TMEDA), and 1,2-dimethoxyethane (glyme). The amount of the polar modifier added depends on the vinyl content desired, the nature of the monomer, the temperature of the polymerization, and the identity of the polar modifier.
The polymers can be optionally hydrogenated. Protecting groups when present on the functionalizing agents and/or initiators can also be optionally removed, prior to or following hydrogenation. Removal of the protecting group(s) (deprotection) produces polymers with at least one functional group (e.g. oxygen, sulfur and/or nitrogen) per polymer chain on the ends of the polymer arms. The functional groups can then participate in various copolymerization reactions by reaction of the functional groups on the ends of the polymer arms with selected difunctional or polyfunctional comonomers.
Deprotection can be performed either prior to or after the optional hydrogenation of the residual unsaturation. For example, to remove tert-alkyl-protected groups, the protected polymer can be mixed with Amberlyst(copyright) 15 ion exchange resin and heated at an elevated temperature, for example 150xc2x0 C., until deprotection is complete. Tert-alkyl-protected groups can also be removed by reaction of the polymer with para-toluensulfonic acid, trifluoroacetic acid, or trimethylsilyliodide. Additional methods of deprotection of the tert-alkyl protecting groups can be found in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, N.Y., 1991, page 41.
Tert-butyldimethylsilyl protecting groups can be removed by treatment of the copolymer with acid, such as hydrochloric acid, acetic acid, para-toluensulfonic acid, or Dowex(copyright) 50W-X8. Alternatively, a source of fluoride ions, for instance tetra-n-butylammonium fluoride, potassium fluoride and 18-crown-6, or pyridine-hydrofluoric acid complex, can be employed for deprotection of the tert-butyldimethylsilyl protecting groups. Additional methods of deprotection of the tert-butyldimethylsilyl protecting groups can be found in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, N.Y., 1991, pages 80-83.
The progress of the deprotection reactions can be monitored by conventional analytical techniques, such as Thin Layer Chromatography (TLC), Nuclear Magnetic Resonance (NMR) spectroscopy, or InfraRed (IR) spectroscopy.
Hydrogenation techniques are described in U.S. Pat. Nos. 4,970,254, 5,166,277, 5,393,843 and 5,496,898, the entire disclosure of each of which is incorporated by reference. The hydrogenation of the polymer is conducted in situ, or in a suitable solvent, such as hexane, cyclohexane or heptane. This solution is contacted with hydrogen gas in the presence of a catalyst, such as a nickel catalyst. The hydrogenation is typically performed at temperatures from 25xc2x0 C. to 150xc2x0 C., with a archetypal hydrogen pressure of 15 psig to 1000 psig. The progress of this hydrogenation can be monitored by InfraRed (IR) spectroscopy or Nuclear Magnetic Resonance (NMR) spectroscopy. The hydrogenation reaction can be conducted until at least 90% of the aliphatic unsaturation has been saturated. The hydrogenated polymer is then recovered by conventional procedures, such as removal of the catalyst with aqueous acid wash, followed by solvent removal or precipitation of the polymer.